U.S. patent number 7,091,298 [Application Number 10/484,300] was granted by the patent office on 2006-08-15 for alcoxy cross-linking, single-component, moisture-hardening materials.
This patent grant is currently assigned to Consortium fuer Elektrochemische Industrie GmbH. Invention is credited to Andreas Bauer, Bernd Pachaly, Wolfram Schindler, Volker Stanjek.
United States Patent |
7,091,298 |
Schindler , et al. |
August 15, 2006 |
Alcoxy cross-linking, single-component, moisture-hardening
materials
Abstract
Alkoxy-crosslinking one-component moisture curing compositions
contain a polymer bearing (alkoxy)(methyl)silylalkyl-terminal
groups, and specific silanes as described herein. The compositions
exhibit improved shelf life and yet retain other desirable
characteristics.
Inventors: |
Schindler; Wolfram (Tussling,
DE), Bauer; Andreas (Kirchdorf, DE),
Stanjek; Volker (Munchen, DE), Pachaly; Bernd
(Mehring, DE) |
Assignee: |
Consortium fuer Elektrochemische
Industrie GmbH (Munich, DE)
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Family
ID: |
7694904 |
Appl.
No.: |
10/484,300 |
Filed: |
July 18, 2002 |
PCT
Filed: |
July 18, 2002 |
PCT No.: |
PCT/EP02/08019 |
371(c)(1),(2),(4) Date: |
January 20, 2004 |
PCT
Pub. No.: |
WO03/014226 |
PCT
Pub. Date: |
February 20, 2003 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20040181025 A1 |
Sep 16, 2004 |
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Foreign Application Priority Data
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Aug 9, 2001 [DE] |
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101 39 132 |
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Current U.S.
Class: |
528/34; 525/342;
525/474 |
Current CPC
Class: |
C08K
5/54 (20130101); C08L 101/10 (20130101); C08K
5/54 (20130101); C08L 101/10 (20130101) |
Current International
Class: |
C08G
77/04 (20060101) |
Field of
Search: |
;528/34
;525/474,342 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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198 49 817 |
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May 2000 |
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DE |
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199 23 300 |
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Nov 2000 |
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DE |
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0 070 475 |
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Jan 1983 |
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EP |
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1 104 787 |
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Jun 2001 |
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EP |
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00/71595 |
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Nov 2000 |
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WO |
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Other References
Derwent Abstract corresponding to DE 199 23 300 AN [2001-081580].
cited by other .
Derwent Abstract corresponding to DE 19849817 AN [2000-351610].
cited by other.
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Primary Examiner: Peng; Kuo-Liang
Attorney, Agent or Firm: Brooks Kushman P.C.
Claims
The invention claimed is:
1. An alkoxy-crosslinking one-component composition, comprising:
(A) at least one alkoxysilane-terminated polymer having terminal
groups of the general formula (1) -A-Si(R).sub.a(CH.sub.3).sub.3-a
(1) and (B) at least one silane selected from the group consisting
of silanes of the formulae (2) to (4)
X--CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a (2)
R''N[CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a].sub.2 (3), and
N[CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a].sub.3 (4) wherein A is a
divalent optionally halogen-substituted C.sub.1-18 hydrocarbon
radical, R is independently methoxy or ethoxy, R'' is hydrogen, an
optionally halogen-substituted cyclic, linear or branched
C.sub.1-18-alkyl or C.sub.6-18-aryl radical, or an R'--O--CO-- or
R'--NH--CO-- radical, R' is an optionally halogen-substituted
C.sub.1-8-hydrocarbon radical, and a is an integer from 1 to 3, and
wherein X is R''O--.
2. The composition of claim 1, wherein an alkoxysilane-terminated
polymer (A) has terminal groups of the general formula (7)
--NR.sup.1--CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a (7) wherein
R.sup.1 is hydrogen or an optionally halogen-substituted C.sub.1-18
alkyl radical or a C.sub.6-18 aryl radical.
3. The composition of claim 2, comprising from 0.1 to 20 parts by
weight of silane(s) (B) per 100 parts by weight of polymer(s)
(A).
4. The composition of claim 3, further comprising at least one as
curing a catalyst component (C) in an amount effective to
accelerate the curing of said composition when exposed to
water.
5. The composition of claim 2, further comprising at least one as
curing a catalyst component (C) in an amount effective to
accelerate the curing of said composition when exposed to
water.
6. The composition of claim 2, wherein at least one polymer (A) is
a polymer selected from the group consisting of polyurethane,
polyether, polyester, polyacrylate, polyvinyl ester,
ethylene/olefin copolymer, styrene/butadiene copolymer and
polyolefin, each of said polymers bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
7. The composition of claim 2, wherein at least one polymer is a
polydiorganosiloxane bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
8. The composition of claim 1, comprising from 0.1 to 20 parts by
weight of silane(s) (B) per 100 parts by weight of polymer(s)
(A).
9. The composition of claim 8, further comprising at least one as
curing a catalyst component (C) in an amount effective to
accelerate the curing of said composition when exposed to
water.
10. The composition of claim 8, wherein at least one polymer (A) is
a polymer selected from the group consisting of polyurethane,
polyether, polyester, polyacrylate, polyvinyl ester,
ethylene/olefin copolymer, styrene/butadiene copolymer and
polyolefin, each of said polymers bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
11. The composition of claim 8, wherein at least one polymer is a
polydiorganosiloxane bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
12. The composition of claim 1, further comprising at least one as
curing a catalyst component (C) in an amount effective to
accelerate the curing of said composition when exposed to
water.
13. The composition of claim 12, wherein at least one polymer (A)
is a polymer selected from the group consisting of polyurethane,
polyether, polyester, polyacrylate, polyvinyl ester,
ethylene/olefin copolymer, styrene/butadiene copolymer and
polyolefin, each of said polymers bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
14. The composition of claim 12, wherein at least one polymer is a
polydiorganosiloxane bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
15. The composition of claim 1, wherein at least one polymer (A) is
a polymer selected from the group consisting of polyurethane,
polyether, polyester, polyacrylate, polyvinyl ester,
ethylene/olefin copolymer, styrene/butadiene copolymer and
polyolefin, each of said polymers bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
16. The composition of claim 1, wherein at least one polymer is a
polydiorganosiloxane bearing terminal
-A-Si(R).sub.a(CH.sub.3).sub.3-a groups.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority to PCT Appln. No. PCT/US02/08019
filed Jul. 18, 2002, and to German application 101 39 132.3 filed
Sep. 8, 2001.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to alkoxy-crosslinking one-component sealant
materials based on alkoxyorganosilane-terminated polymers having an
outstanding shelf-life and outstanding curing characteristics.
2. Description of the Related Art
Organic polymers having terminal silane groups in the form of
one-component materials curing with atmospheric humidity (RTV-1)
are known and are widely used for the preparation of flexible
sealants and adhesives. Such polymers may be composed of different
building blocks. Usually, these are polyurethanes, polyethers,
polyesters, polyacrylates, polyvinyl esters, ethylene/olefin
copolymers, styrene/butadiene copolymers or polyolefins. It is
known that, for stabilization during the processing and storage of
the compounds, low molecular weight compounds which have
hydrolyzable groups which have a higher reactivity to water than
the silane-terminated polymers are added to these one-component
materials. The amount of added water scavengers depends on the
water content of the components of the formulation and on the
desired shelf-lives and processing times. In general, these are
organofunctional silanes, the organic radical often being critical
for the reactivity. Examples of such silanes are
vinyltrimethoxysilane and alkylaminopropyltrimethoxysilanes, but
also, for example, silanes which bind water with the formation of
ammonia, such as hexamethyldisilazane.
In general, substituted propyltrimethoxysilanes are used for the
termination since they are as a rule economically available and
have very good reactivity in the materials. However, owing to the
high reactivity, the polymers are also problematic with regard to
processing, for example in the incorporation of water-containing
fillers or additives which increase the reactivity further;
moreover, the shelf-lives are often insufficient.
For example, the addition of relatively large amounts of
aminosilanes as adhesion promoters can greatly reduce the
shelf-life. The materials generally have to be stabilized by means
of further added components, such as, for example, the phosphoric
esters described in DE-A-19923300, in order to moderate the
catalyst activity. Furthermore, the addition of standard water
scavengers, such as vinyltrimethoxysilane, is suitable only to a
limited extent for stabilizing the materials.
Analogously to the organic polymers already described above,
polydiorganosiloxanes having high reactivities are also known. U.S.
Pat. No. 5,254,657 describes moisture-curing silicone-based
materials in which the crosslinkable silane units are prepared
analogously to the organic polymers via the reaction of an
aminosilicone with an isocyanatoalkylalkoxysilane. These too have a
problematic shelf-life owing to the high reactivity of the terminal
silane groups.
SUMMARY OF THE INVENTION
It has now been surprisingly discovered that alkoxy-crosslinking
one-component moisture-curing materials with improved shelf life
characteristics, yet which retain desirable curing characteristics,
may be prepared from (alkoxy)(methyl)silyalkyl-terminated polymers
and specific silanes, as described hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
The invention relates to alkoxy-crosslinking one-component
materials which comprise (A) alkoxysilane-terminated polymer having
terminal groups of the general formula (1)
-A-Si(R).sub.a(CH.sub.3).sub.3-a (1) and (B) silane which is
selected from silanes of the general formulae (2) to (4)
X--CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a (2)
R''N[CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a].sub.2 (3)
N[CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a].sub.3 (4) in which A is
a divalent optionally halogen-substituted hydrocarbon radical
having 1 to 18 C atoms, R is a methoxy or ethoxy group, X is an
R''O-- or R''NH-- group or halogen, R'' is hydrogen, an optionally
halogen-substituted cyclic, linear or branched C.sub.1-18-alkyl or
C.sub.6-18-aryl radical, or an R'--O--CO-- or R'--NH--CO-- radical,
R' is an optionally halogen-substituted C.sub.1-8-hydrocarbon
radical and a is an integer from 1 to 3.
The materials based on alkoxyorganosilane-terminated polymers (A)
have an excellent shelf-life and excellent curing characteristics.
It has in fact been found that the addition of silanes of the
general formulae (2) to (4) to polymers (A) is suitable for
preparing such materials having an improved shelf-life without
having an adverse effect on the kinetics of curing and the complete
curing of materials. With regard to the processing, the materials
are processible for a sufficiently long time without gelling, owing
to the very high reactivity of the silanes of the general formulae
(2) to (4), in contrast to the compositions to date. The processing
time can be adjusted by the added amount of silane. However,
because the silanes of the general formulae (2) to (4) have a
sufficiently high reactivity, the skin formation and complete
curing times are only slightly dependent on the amount of silane.
Thus, it is possible to prepare materials which are very well
stabilized to relatively large amounts of water, which emerge, for
example, from the fillers during storage, without adversely
affecting the curing characteristics.
The preparation of various silane-terminated polymers (A) is
described, for example, in U.S. Pat. No. 3,971,751, EP-A-70475,
DE-A-19849817, U.S. Pat. No. 6,124,387 or U.S. Pat. No. 5,990,257.
Various products are commercially available, such as MS-Polymer
S203H and S303H (from Kaneka Corp.), Desmoseal.RTM. LS 2237 (Bayer
AG), Polymer ST50 (Hanse-Chemie GmbH), Excestar.RTM. S2410 and
S2420 (Asahi Glass), Permapol.RTM. MS (Courtaulds Coatings Inc.) or
WSP 725-80 (Witton Chemical Co.). In addition, further
silane-terminated polymers (A) having an organic polymer skeleton
can also be used.
The polymers (A) preferably contain a skeleton comprising
polyurethane, polyether, polyester, polyacrylate, polyvinyl ester,
ethylene/olefin copolymer, styrene/butadiene copolymer or
polyolefin. Polyethers, polyesters and polyurethanes having molar
masses Mn of 5 000 50 000, in particular 10 000 25 000, are
particularly preferred. The viscosities of the polymers (A) are
preferably not more than 200 Pas, in particular not more than 100
Pas.
In the above general formulae (1) to (4): R'' is preferably
hydrogen, a cyclic or linear C.sub.1-6-alkyl or C.sub.6-10-aryl
radical, especially butyl, cyclohexyl or phenyl, R' is preferably a
C.sub.1-4-alkyl or phenyl radical; especially methyl or ethyl, A is
preferably a branched or linear C.sub.1-6-alkyl radical, in
particular a methylene or a trimethylene group, a preferably has
the values 2 or 3.
A multiplicity of possibilities is known for the preparation of
silane-terminated polymers (A), in particular: Copolymerization of
unsaturated monomers with those which have, for example,
alkoxysilyl groups, such as vinyltrimethoxysilane. Grafting of
unsaturated monomers, such as vinyltrimethoxysilane, onto
thermoplastics, such as polyethylene. The addition of H-silanes,
such as methyldimethoxysilane, at the carbon double bonds under
noble metal catalysis. Reaction of organosilanes with the
prepolymer. Here, a functional group of the prepolymer is reacted
with a functional group of the silane.
The frequently adopted and simplest route for the last-mentioned
case is a reaction of NCO groups of an isocyanate prepolymer with
an aminosilane of the general formula (5):
R.sup.1--NH-A-Si(R).sub.a(CH.sub.3).sub.3-a (5)
Accordingly, OH groups of an isocyanate prepolymer, but also of a
very wide range of other parent polymer building blocks, such as,
for example, pure polyethers, can furthermore be reacted with an
isocyanatosilane of the general formula (6):
OCN-A-Si(R).sub.a(CH.sub.3).sub.3-a (6)
In the general formulae (5) and (6), R.sup.1 is hydrogen or an
optionally halogen-substituted alkyl radical having 1 to 18, in
particular 1 to 6, C atoms, or an aryl radical having 6 to 18, in
particular 6 to 10, C atoms, A, R and a have the above
meanings.
Preferably, A is trimethylene, R is methoxy, R.sup.1 is phenyl or a
linear alkyl radical, such as ethyl or butyl, and a has the value
3.
In a preferred embodiment, the alkoxysilane-terminated polymer (A)
has terminal groups of the general formula (7)
--NR.sup.1--CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a (7).
This can be prepared analogously to the process described above by
reacting NCO groups of an isocyanate prepolymer with an aminosilane
of the general formula (8):
R.sup.1NH--CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a (8)
Accordingly, OH groups of an isocyanate prepolymer, but also of a
very wide range of other parent polymer building blocks, such as,
for example, pure polyethers, can furthermore be reacted with an
isocyanatosilane of the general formula (9).
OCN--CH.sub.2--Si(R).sub.a(CH.sub.3).sub.3-a (9)
In the general formulae (7) and (8) and (9), R.sup.1, R and a have
the above meanings. Preferably, R.sup.1 is phenyl or a linear alkyl
radical, such as ethyl or butyl, and a has the values 2 or 3.
In the case of silane-terminated polymers (A) having terminal
groups of the general formula (7), it has been found that, owing to
their very high reactivity, they can be compounded only with very
great difficulty. The water content of conventional fillers and
additives is often sufficient to lead to complete gelling of the
material during the compounding or to substantial stiffening, which
generally results in materials which can be scarcely processed.
Furthermore, these materials are problematic with regard to their
shelf-life and cannot be stored for a long time. During the
processing of these RTV-1 mixtures, the materials attract moisture
so rapidly that uniform processing is impossible. The attempt to
stabilize these materials with the standard water scavengers
described above was unsuccessful.
In contrast to the water scavengers to date, silane-terminated
polymers (A) according to the general formula (7) can be stabilized
for a sufficiently long time without gelling, owing to the very
high reactivity of the silanes of the general formulae (2), (3) and
(4). Here too, the processing time can be adjusted by the added
amount of silane. However, the processing times and the tack-free
and complete curing times are substantially shorter. Thus, fast
RTV-1 materials having a long shelf-life and comprising
silane-terminated polymers (A) according to the general formula (7)
can now also be prepared.
Polymers having a skeleton comprising polydiorganosiloxane and
terminal groups of the general formula (1) can also be used as
polymers (A). Silanes of the general formula (6) are preferably
subjected to an addition reaction with silicone oils having
terminal hydroxyalkyl or aminoalkyl groups.
Conventional silicone polymers, prepared by blocking of
Si--OH-terminated silicone oils with alkoxy-functional silanes,
such as vinyltrimethoxysilane or methyltrimethoxysilane, can also
be used as a further embodiment instead of the polymers (A).
Organofunctional silanes of the general formulae (2), (3) and (4)
having methylene spacers can be used as component (B). Examples of
such silanes are aminomethyltrimethoxysilane,
aminomethylmethyldimethoxysilane, bis(trimethoxysilylmethyl)amine,
aminomethyltriethoxysilane, aminomethylmethyldiethoxysilane,
bis(triethoxysilylmethyl)amine, phenylaminomethyltrimethoxysilane,
phenylaminomethylmethyldimethoxysilane,
butylaminomethyltrimethoxysilane,
butylaminomethyl-methyldimethoxysilane,
cyclohexylaminomethyltrimethoxysilane,
cyclohexylaminomethyl-methyldimethoxysilane,
methoxymethyltrimethoxysilane, methoxymethyl-methyldimethoxysilane,
ethoxymethyltriethoxysilane, ethoxymethylmethyldiethoxysilane,
methylcarbamatomethyltrimethoxysilane,
methylcarbamatomethyl-methyldimethoxysilane,
ethylcarbamatomethyltriethoxysilane,
ethylcarbamatomethyl-methyldiethoxysilane,
chloromethyltrimethoxysilane and
chloromethylmethyldimethoxysilane.
Aminomethyltrimethoxysilane and aminomethylmethyldimethoxysilane
are preferred, and phenylaminomethyltrimethoxysilane,
phenylaminomethylmethyldimethoxysilane,
methoxymethyltrimethoxysilane and
methoxymethyl-methyldimethoxysilane,
methylcarbamatomethyltrimethoxysilane,
methylcarbamatomethylmethyldimethoxysilane,
ethylcarbamatomethyltriethoxysilane,
ethylcarbamatomethyl-methyldiethoxysilane, which have no additional
accelerating effect on the reactivity owing to their lower
basicity, are particularly preferred.
The materials preferably contain from 0.1 to 20 parts by weight,
particularly preferably from 0.5 to 10 parts by weight, in
particular from 2 to 6 parts by weight, of silanes (B) per 100
parts by weight of polymer (A).
The materials may contain, as component (C), a catalyst for curing.
Preferably, all organometallic catalysts which are known to promote
silane condensation can be used as component (C). These are in
particular tin compounds and titanium compounds. Preferred tin
compounds are dibutyltin dilaurate, dibutyltin diacetate and
dibutyltin bisacetylacetonate. Preferred titanium compounds are
alkyl titantates, such as tetraisoproyl titanate and tetrabutyl
titanate. Furthermore, basic amines can be used as cocatalysts but,
where suitable, also as the catalyst itself. For example, compounds
such as 1,8-diazabicyclo-[5.4.0]undec-7-ene or
4-dimethylaminopyridine are preferred. Furthermore, organic
nitrogen compounds which carry at least one silyl group may also be
used. Suitable bases having a silyl group are, for example, silanes
containing amino groups, such as aminopropyltrimethoxysilane,
aminopropyltriethoxysilane, aminomethyltrimethoxysilane,
aminomethyltriethoxysilane, aminoethylaminopropyltrimethoxysilane,
butylaminopropyltrimethoxysilane, butylaminomethyltrimethoxysilane,
cyclohexylaminomethyltrimethoxysilane and
cyclohexylaminopropyltrimethoxysilane.
The materials may furthermore contain, as component (D), assistants
known per se, such as adhesion promoters, plasticizers, fillers,
thixotropic agents, light stabilizers, fungicides and pigments,
which are known for use in alkoxy-crosslinking one-component
materials.
All above symbols of the above formulae have their meanings in each
case independently of one another. In all formulae, the silicon
atom is tetravalent.
The following examples serve for illustrating the invention without
restricting it. Unless stated otherwise, all stated amounts and
percentages are based on weight, all pressures are 0.10 MPa (abs.)
and all temperatures are 20.degree. C.
EXAMPLES
Preparation of Isocyanatomethyltrimethoxysilane:
Starting from chloromethyltrimethoxysilane,
methylcarbamatomethyltrimethoxysilane is synthesized according to
known processes (U.S. Pat. No. 3,494,951).
This is pumped in an argon gas stream into a quartz pyrolysis tube
filled with quartz wool. The temperature in the pyrolysis tube is
between 420 and 470 C. At the end of the heated zone, the crude
product is condensed with the aid of a condenser and collected. The
colorless liquid is purified by distillation under reduced
pressure. The desired product passes over at the top at about 88 90
C (82 mbar) in more than 99% purity, while the unreacted carbamate
can be reisolated in the bottom. This is recycled directly to the
pyrolysis.
Starting from 56.9 g (273 mmol) of
methylcarbamatomethyltrimethoxysilane, 33.9 g (191 mmol) of the
desired product isocyanatomethyl-trimethoxysilane are contained in
this manner in a purity>97%. This corresponds to a yield of 70%
of theory.
Preparation of N-phenylaminomethyltrimethoxysilane:
537 g (5.77 mol) of aniline are initially completely introduced
into a laboratory reactor and then blanketed with nitrogen. Heating
to a temperature of 115.degree. C. is effected and 328 g (1.92 mol)
of chloromethyltrimethoxysilane are added dropwise over 1.5 h and
stirring is effected for a further 30 minutes at 125 130.degree. C.
After an addition of about 150 g of the silane, anilinium
hydrochloride is increasingly precipitated as the salt, but the
suspension remains readily stirrable until the end of the metering.
Aniline used in excess (about 180 g) is removed under a good vacuum
(62.degree. C. at 7 mbar). Thereafter, 350 ml of toluene are added
at about 50.degree. C. and the suspension is stirred for 30 min at
10.degree. C. in order to crystallize aniline hydrochloride
completely. This is then filtered off. The solvent toluene is
removed under a partial vacuum at 60 70.degree. C. The residue is
purified by distillation (89 91.degree. C. at 0.16 mbar).
A yield of 331 g, i.e. 75.9% of theory, is achieved at a product
purity of about 96.5%. The product contains about 3.5% of
N,N-bis[trimethoxysilylmethyl]phenylamine as an impurity.
Preparation of Methoxymethyltrimethoxysilane:
340 g (6.3 mol) of sodium methylate (95% strength) are dissolved in
portions in 2.5 l of methanol in a laboratory reactor blanketed
with nitrogen. During this procedure, the solution heats up to
65.degree. C. Thereafter, 995 g (5.8 mol) of
chloromethyltrimethoxysilane are added dropwise over 1.5 h and
stirring is effected for a further 30 minutes at the boil. On
addition of the silane, sodium chloride is precipitated
spontaneously as the salt, but the suspension remains readily
stirrable until the end of the metering. The precipitated sodium
chloride is filtered off with suction and the methanol is removed
under a partial vacuum at 40 50.degree. C. The residue is purified
by distillation (97 98.degree. C. at 172 mbar).
A yield of 678.0 g, i.e. 70.3% of theory, is achieved at a product
purity of about 99.5%.
Example 1 (Comparative Example)
400 g of a polypropylene glycol having an average molecular weight
of 8,000 g/mol are polymerized with 23.0 g of isophorone
diisocyanate at 100.degree. C. in the course of 60 min. The
polyurethane prepolymer obtained is then cooled to 60.degree. C.
and mixed with 12.8 g of phenylaminopropyltrimethoxysilane
(obtainable from CK-Witco under Silquest.RTM. Y-9669) and stirred
for 60 min until an isocyanate band is no longer visible in the IR
spectrum. The silane-terminated polymer thus obtained is mixed, at
about 25.degree. C., with 155 g of diisoundecyl phthalate, 21.0 g
of 3-(2-aminoethyl)aminopropyl-trimethoxysilane, 21.0 g of
vinyltrimethoxysilane and 435 g of precipitated and dried chalk
(water content <300 ppm) and processed in the course of 0.5 h in
a laboratory planetary mixer to give a firm paste. Finally, 2.0 g
of dibutyltin dilaurate are mixed in as a catalyst in the course of
10 min. A part of the paste is applied with a layer thickness of 5
mm to a Teflon sheet by means of a doctor blade and crosslinked
under the action of atmospheric humidity to give a resilient
rubber. The tack-free times and the complete curing of the specimen
are determined (23.degree. C./50% relative humidity).
A further part of the paste is introduced into aluminum cartridges
and stored for 4 days at 70.degree. C. Thereafter, the consistency
is tested and the tack-free times and the complete curing are
determined as described above. The characteristics of the product
are listed in table 1.
Example 2
A silane-terminated polymer prepared according to example 1 is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 21.0 g of
methoxymethyltrimethoxysilane and 435 g of precipitated and dried
chalk (water content<300 ppm) and processed in the course of 0.5
h in a laboratory planetary mixer to give a firm paste. Finally,
2.0 g of dibutyltin dilaurate are mixed in as a catalyst in the
course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 3
A silane-terminated polymer prepared according to example 1 is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 42.0 g of
methoxymethyltrimethoxysilane and 435 g of precipitated and dried
chalk (water content<300 ppm) and processed in the course of 0.5
h in a laboratory planetary mixer to give a firm paste. Finally,
2.0 g of dibutyltin dilaurate are mixed in as a catalyst in the
course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 4
A silane-terminated polymer prepared according to example 1 is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 42.0 g of
phenylaminomethyltrimethoxysilane and 435 g of precipitated and
dried chalk (water content<300 ppm) and processed in the course
of 0.5 h in a laboratory planetary mixer to give a firm paste.
Finally, 2.0 g of dibutyltin dilaurate are mixed in as a catalyst
in the course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 5 (Comparative Example)
300 g of Desmoseal.RTM. LS 2237 (silane-terminated polyurethane,
obtainable from Bayer AG) are mixed at about 25.degree. C. with 108
g of diisoundecyl phthalate, 16.7 g of
3-(2-aminoethyl)aminopropyltrimethoxysilane, 16.7 g of
vinyltrimethoxysilane and 328 g of precipitated and dried chalk
(water content<300 ppm) and processed in the course of 0.5 h in
a laboratory planetary mixer to give a firm paste. Finally, 2.0 g
of dibutyltin dilaurate are mixed in as a catalyst in the course of
10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 6
300 g of Desmoseal.RTM. LS 2237 are mixed at about 25.degree. C.
with 108 g of diisoundecyl phthalate, 16.7 g of
3-(2-aminoethyl)aminopropyltrimethoxysilane, 16.7 g of
methoxymethyltrimethoxysilane and 328 g of precipitated and dried
chalk (water content<300 ppm) and processed in the course of 0.5
h in a laboratory planetary mixer to give a firm paste. Finally,
2.0 g of dibutyltin dilaurate are mixed in as a catalyst in the
course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 7
300 g of Desmoseal.RTM. LS 2237 are mixed at about 25.degree. C.
with 108 g of diisoundecyl phthalate, 16.7 g of
3-(2-aminoethyl)aminopropyltrimethoxysilane, 33.4 g of
methoxymethyltrimethoxysilane and 328 g of precipitated and dried
chalk (water content<300 ppm) and processed in the course of 0.5
h in a laboratory planetary mixer to give a firm paste. Finally,
2.0 g of dibutyltin dilaurate are mixed in as a catalyst in the
course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 8
300 g of Desmoseal.RTM. LS 2237 are mixed at about 25.degree. C.
with 108.0 g of diisoundecyl phthalate, 16.7 g of
3-(2-aminoethyl)aminopropyltrimethoxysilane, 16.7 g of
phenylaminomethyltrimethoxysilane and 328 g of precipitated and
dried chalk (water content<300 ppm) and processed in the course
of 0.5 h in a laboratory planetary mixer to give a firm paste.
Finally, 2.0 g of dibutyltin dilaurate are mixed in as a catalyst
in the course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 9 (Comparative Example)
500 g of .alpha.,.omega.-aminopropylpolydimethylsiloxane having an
average molecular weight of 15,000 g/mol are heated to 80.degree.
C. in a heatable laboratory planetary mixer provided with a vacuum
pump and are heated to completion in the course of 0.5 h in vacuo.
After cooling to 30 35.degree. C., 16.4 g of
isocyanatopropyltrimethoxysilane (obtainable from CK-Witco under
Silquest.RTM. Y-5187) are added and stirring is effected for a
further 30 min. The silane-terminated polymer thus obtained is
mixed at about 25.degree. C. with 230 g of a
trimethylsilyl-terminated polydimethylsiloxane having a viscosity
of 100 Pas, 16.7 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane,
16.7 g of vinyltrimethoxysilane and 85 g of a hydrophilic pyrogenic
silica (obtainable from Wacher-Chemie-GmbH under HDK.RTM.-V15) and
processed in the course of 0.5 h to give a firm paste. Finally,
0.75 g of dibutyltin dilaurate is mixed in as a catalyst in the
course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 10
A silane-terminated polymer prepared according to example 8 is
mixed at about 25.degree. C. with 230 g of a
trimethylsilyl-terminated polydimethylsiloxane having a viscosity
of 100 Pas, 16.7 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane,
16.7 g of methoxymethyltrimethoxysilane and 85 g of a hydrophilic
pyrogenic silica and processed in the course of 0.5 h to give a
firm paste. Finally, 0.75 g of dibutyltin dilaurate is mixed in as
a catalyst in the course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 11
A silane-terminated polymer prepared according to example 8 is
mixed at about 25.degree. C. with 230 g of a
trimethylsilyl-terminated polydimethylsiloxane having a viscosity
of 100 Pas, 16.7 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane,
33.4 g of methoxymethyltrimethoxysilane and 85 g of a hydrophilic
pyrogenic silica and processed in the course of 0.5 h to give a
firm paste. Finally, 0.75 g of dibutyltin dilaurate is mixed in as
a catalyst in the course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 12
A silane-terminated polymer prepared according to example 8 is
mixed at about 25.degree. C. with 230 g of a
trimethylsilyl-terminated polydimethylsiloxane having a viscosity
of 100 Pas, 16.7 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane,
16.7 g of phenylaminomethyltrimethoxysilane and 85 g of a
hydrophilic pyrogenic silica and processed in the course of 0.5 h
to give a firm paste. Finally, 0.75 g of dibutyltin dilaurate is
mixed in as a catalyst in the course of 10 min.
The tack-free times, the complete curing and the shelf-life are
determined as described above. The characteristics of the product
are listed in table 1.
Example 13 (Comparative Example)
400 g of a polypropylene glycol having an average molecular weight
of 8 000 g/mol are polymerized with 23.0 g of isophorone
diisocyanate at 100.degree. C. in the course of 60 min. The
polyurethane prepolymer obtained is then cooled to 60.degree. C.
and mixed with 10.5 g of phenylaminomethyltrimethoxysilane and
stirred for 60 min until an isocyanate band is no longer visible in
the IR spectrum. The silane-terminated polymer thus obtained is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 21.0 g of
vinyltrimethoxysilane and 435 g of precipitated and dried chalk
(water content<300 ppm) and processed in a laboratory planetary
mixer to give a firm paste. The product gels as early as when the
fillers are incorporated.
Example 14 (Comparative Example)
A silane-terminated polymer prepared according to example 13 is
compounded as described there, using 63.0 g of
vinyltrimethoxysilane. The product could still be processed in the
laboratory planetary mixer to give a firm paste but has
spontaneously cured completely during the production of the test
specimens.
Example 15 (Comparative Example)
400 g of a polypropylene glycol having an average molecular weight
of 8,000 g/mol are polymerized with 12.5 g of isophorone
diisocyanate at 100.degree. C. in the course of 60 min. The
polyurethane prepolymer obtained is then cooled to 60.degree. C.
and mixed with 19.7 g of isocyanatomethyltrimethoxysilane and
stirred for 60 min until an isocyanate band is no longer visible in
the IR spectrum. The silane-terminated polymer thus obtained is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyl-trimethoxysilane, 21.0 g of
vinyltrimethoxysilane and 435 g of precipitated and dried chalk
(water content<300 ppm) and processed in a laboratory planetary
mixer to give a firm paste. The product gels as early as when the
fillers are incorporated.
Example 16
A silane-terminated polymer prepared according to example 13 is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 21.0 g of
methoxymethyltrimethoxysilane and 435 g of precipitated and dried
chalk (water content<300 ppm) and processed in a laboratory
planetary mixer to give a firm paste. The tack-free times, the
complete curing and the shelf-life are determined as described
above. The characteristics of the product are listed in table
1.
Example 17
A silane-terminated polymer prepared according to example 13 is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 42.0 g of
methoxymethyltrimethoxysilane and 435 g of precipitated and dried
chalk (water content<300 ppm) and processed in a laboratory
planetary mixer to give a firm paste. The tack-free times, the
complete curing and the shelf-life are determined as described
above. The characteristics of the product are listed in table
1.
Example 18
A silane-terminated polymer prepared according to example 13 is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 21.0 g of
phenylaminomethyltrimethoxysilane and 435 g of precipitated and
dried chalk (water content<300 ppm) and processed in a
laboratory planetary mixer to give a firm paste. The tack-free
times, the complete curing and the shelf-life are determined as
described above. The characteristics of the product are listed in
table 1.
Example 19
A silane-terminated polymer prepared according to example 15 is
mixed at about 25.degree. C. with 155 g of diisoundecyl phthalate,
21.0 g of 3-(2-aminoethyl)aminopropyltrimethoxysilane, 42.0 g of
methoxymethyltrimethoxysilane and 435 g of precipitated and dried
chalk (water content<300 ppm) and processed in a laboratory
planetary mixer to give a firm paste. The tack-free times, the
complete curing and the shelf-life are determined as described
above. The characteristics of the product are listed in table
1.
TABLE-US-00001 TABLE 1 Curing characteristics and shelf-life of the
moisture-curing materials Tack- Complete Tack- Complete free curing
free curing 4d/60.degree. C. 4d/60.degree. C. Shelf-life Example
[min] [mm/d] [min] [mm/d] (remark) Example 1 60 2 3 35 2 Paste
(comparison) substantially more viscous Example 2 40 3 40 2 3 Paste
slightly more viscous Example 3 45 3 40 3 Paste unchanged Example 4
50 2 3 45 2 3 Paste unchanged Example 5 70 3 4 45 2 3 Paste
(comparison) substantially more viscous Example 6 60 3 4 55 3 4
Paste unchanged Example 7 65 3 4 65 3 4 Paste unchanged Example 8
65 3 4 55 4 Paste slightly more viscous Example 9 15 5 6 5 10 12
Paste (comparison) substantially more viscous Example 10 15 6 7 10
6 7 Paste slightly more viscous Example 11 15 6 7 15 6 7 Paste
unchanged Example 12 15 6 7 15 6 7 Paste unchanged Example 16 4
>15 3 >15 Paste slightly more viscous Example 17 7 >15 6
>15 Paste unchanged Example 18 4 >15 3 >15 Paste slightly
more viscous Example 19 6 >15 5 >15 Paste unchanged
Example 20
500 g of an .alpha.,.omega.-OH-terminated polypropylene glycol
having an average molecular weight of 12,000 g/mol are reacted with
17.7 g of isocyanatomethyltrimethoxysilane at 90.degree. C. in the
course of 60 min with addition of 130 mg of dibutyltin dilaurate.
The silane-terminated polyether thus obtained is mixed with a
further 10.5 g of a silane (cf. table 2) and stored in air. The
viscosity of the polymer is determined as a function of time.
Depending on added silane, an increase in the viscosity in air at
different rates as a result of condensation of the polymer by means
of atmospheric humidity is observed, the silanes used according to
the invention leading to substantially higher stabilization of the
polymer.
TABLE-US-00002 TABLE 2 Viscosity increase of a silane-terminated
polyether under the action of atmospheric humidity depending on the
silane used (2.0% by weight each) Viscosity [Pa s] Time (days) 0 1
2 3 Methylcarbamatomethyl- 12 11 14 24 trimethoxysilane
Methoxymethyltri- 12 13 19 30 methoxysilane Vinyltrimethoxysilane
12 15 30 45 (not according to the (tack-free) invention)
Methyltrimethoxysilane 13 19 47 -- (not according to the
(tack-free) invention) No addition 13 26 53 -- (tack-free)
* * * * *